Dimethyl Sulfoxide → N-(tert-Butoxycarbonyl)-D-prolinal

HRID 846660Notes

Reaction equation

HRID 846660 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[OH:11][CH2:12][C@H:13]1[CH2:17][CH2:16][CH2:15][N:14]1[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19].C(N(CC)CC)C>C(Cl)Cl.O>[CH:12]([C@H:13]1[CH2:17][CH2:16][CH2:15][N:14]1[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])=[O:11]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 688279N-(tert-Butoxycarbonyl)-D-prolinol

Product 1

HCID 7009153N-(tert-Butoxycarbonyl)-D-prolinalYield 95%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

Oxalyl chloride (12.0 ml, 0.14 mol) was added dropwise with stirring to methylene chloride (200 mL) at -78° C., under nitrogen. Ten min. after addition was complete, DMSO (20 mL) was slowly added and stirring was continued for an additional 10 min. (R)-t-Butyl 2-(hydroxymethyl)-1-pyrrolidinecarboxylate (15.0 g, 0.075 mol) in methylene chloride was added to the stirred solution and after 30 min triethylamine (56 mL) was added. The solution was held at -78° C. for 30 min. and was then allowed to warm to room temperature. Water (100 mL) was added, the phases separated, and the aqueous phase reextracted with methylene chloride (200 mL). The combined organic phases were washed with water (30 mL), evaporated, and the residual oil was chromatographed on silica gel using ethyl acetate:Skellysolve B (1:2) as eluant to give 14.2 g (95%) of product.

Workup

  1. additionTen min. after addition
  2. additionwas added
  3. waitThe solution was held at -78° C. for 30 min.
  4. customthe phases separated
  5. washThe combined organic phases were washed with water (30 mL)
  6. customevaporated
  7. customthe residual oil was chromatographed on silica gel

Sources & evidence

ORD record
ord-2f3219258cd147f39870c00b74b82560
Source dataset
uspto-grants-1992_08
Patent number
US05137905

Reaction notes

Loading…